Cleaning compositions for removing residues on semiconductor substrates

ABSTRACT

This disclosure relates to a cleaning composition that contains 1) at least one redox agent; 2) at least one water soluble organic solvent; 3) at least one metal-containing additive; 4) at least one cyclic amine, and 5) water.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims priority to U.S. Provisional ApplicationSer. No. 62/475,947, filed on Mar. 24, 2017, which is herebyincorporated by reference in its entirety.

BACKGROUND 1. Field of the Disclosure

The present disclosure relates to novel cleaning compositions forsemiconductor substrates and methods of cleaning semiconductorsubstrates. More particularly, the present disclosure relates tocleaning compositions for semiconductor substrates after plasma etchingof metal layers or dielectric material layers deposited on thesubstrates and the removal of residues left on the substrates after bulkresist removal via a plasma ashing process.

2. Discussion of the Background Art

In the manufacture of integrated circuit devices, photoresists are usedas an intermediate mask for transferring the original mask pattern of areticle onto the wafer substrate by means of a series ofphotolithography and plasma etching steps. One of the essential steps inthe integrated circuit device manufacturing process is the removal ofthe patterned photoresist films from the wafer substrate. In general,this step is carried out by one of two methods.

One method involves a wet stripping step in which thephotoresist-covered substrate is brought into contact with a photoresiststripper solution that consists primarily of an organic solvent and anamine. However, stripper solutions cannot completely and reliably removethe photoresist films, especially if the photoresist films have beenexposed to UV radiation and plasma treatments during fabrication. Somephotoresist films become highly crosslinked by such treatments and aremore difficult to dissolve in the stripper solution. In addition, thechemicals used in these conventional wet-stripping methods are sometimesineffective for removing inorganic or organometallic residual materialsformed during the plasma etching of metal or oxide layers withhalogen-containing gases.

An alternative method of removing a photoresist film involves exposing aphotoresist-coated substrate to oxygen-based plasma in order to burn theresist film from the substrate in a process known as plasma ashing.However, plasma ashing is also not fully effective in removing theplasma etching by-products noted above. Instead, removal of these plasmaetch by-products is typically accomplished by subsequently exposing theprocessed metal and dielectric thin films to certain cleaning solutions.

Metal substrates are generally susceptible to corrosion. For example,substrates such as aluminum, copper, aluminum-copper alloy, tungstennitride, tungsten (W), cobalt (Co), titanium oxide, other metals andmetal nitrides, can readily corrode and dielectrics [ILD, ULK] can beundesirably etched by using conventional cleaning chemistries. Inaddition, the amount of corrosion tolerated by the integrated circuitdevice manufacturers is getting smaller and smaller as the devicegeometries shrink.

At the same time, as residues become harder to remove and corrosion mustbe controlled to ever lower levels, cleaning solutions should be safe touse and environmentally friendly.

Therefore, the cleaning solution should be effective for removing theplasma etch and plasma ashing residues and should also be non-corrosiveto all exposed substrate materials.

SUMMARY OF THE DISCLOSURE

The present disclosure is directed to non-corrosive cleaningcompositions that are useful for removing residues (e.g., plasma etchand/or plasma ashing residues) from a semiconductor substrate as anintermediate step in a multistep manufacturing process. These residuesinclude a range of relatively insoluble mixtures of organic compoundssuch as residual photoresist; organometallic compounds; metal oxidessuch as aluminum oxides (AlOx), titanium oxides (TiOx), zirconium oxides(ZrOx), tantalum oxides (TaOx), and hafnium oxides (HfOx) (which can beformed as reaction by-products from exposed metals); metals such asaluminum (Al), aluminum/copper alloy, copper (Cu), titanium (Ti),tantalum (Ta), tungsten (W), and cobalt (Co); metal nitrides such asaluminum nitrides (AlN), aluminum oxide nitrides (AlOxNy), titaniumnitrides (TiN), tantalum nitrides (TaN), and tungsten nitrides (WN);their alloys; and other materials. An advantage of the cleaningcomposition described herein is that it can clean a broad range ofresidues encountered and be generally non-corrosive to exposed substratematerials (e.g., exposed metals (such as aluminum, aluminum/copperalloy, copper, titanium, tantalum, tungsten, and cobalt), metal nitrides(such as titanium, tantalum, and tungsten nitrides), and their alloys).

In one aspect, the present disclosure features a cleaning compositioncontaining

1) at least one redox agent;

2) at least one water soluble organic solvent;

3) at least one metal-containing additive;

4) at least one cyclic amine; and

5) water.

The present disclosure also features a method of cleaning residues froma semiconductor substrate. The method includes contacting asemiconductor substrate containing post etch residues and/or post ashingresidues with a cleaning composition described herein. For example, themethod can include the steps of: (A) providing a semiconductor substratecontaining post etch and/or post ashing residues; (B) contacting saidsemiconductor substrate with a cleaning composition described herein;(C) rinsing said semiconductor substrate with a suitable rinse solvent;and (D) optionally, drying said semiconductor substrate by any meansthat removes the rinse solvent and does not compromise the integrity ofsaid semiconductor substrate.

DETAILED DESCRIPTION OF THE DISCLOSURE

As defined herein, unless otherwise noted, all percentages expressedshould be understood to be percentages by weight to the total weight ofthe cleaning composition. Unless otherwise noted, ambient temperature isdefined to be between about 16 and about 27 degrees Celsius (° C.), suchas 25° C.

The terms “layer” and “film” are used interchangeably.

As defined herein, a “water-soluble” substance (e.g., a water-solublealcohol, ketone, ester, sulfones, or ether) refers to a substance havinga solubility of at least 5% by weight in water at 25° C.

One embodiment of the present disclosure is directed to a non-corrosivecleaning composition including:

1) at least one redox agent;

2) at least one water soluble organic solvent (e.g., a water solubleorganic solvent selected from the group consisting of water solublealcohols, water soluble ketones, water soluble esters, water solublesulfones, and water soluble ethers);

3) at least one metal-containing additive;

4) at least one cyclic amine; and

5) water.

The compositions of this disclosure contain at least one redox agent,which is believed to aid in the dissolution of residues on thesemiconductor surface such as photoresist residues, metal residues, andmetal oxide residues. As used herein, the term “redox agent” refers to acompound that can induce an oxidation and/or a reduction in asemiconductor cleaning process. An example of a suitable redox agent ishydroxylamine. In some embodiments, the redox agent or the cleaningcomposition described herein does not include a peroxide (e.g., hydrogenperoxide).

In some embodiments, the compositions of this disclosure include atleast about 0.5% by weight (e.g., at least about 1% by weight, at leastabout 2% by weight, at least about 3% by weight, or at least about 5% byweight) and/or at most about 20% by weight (e.g., at most about 17% byweight, at most about 15% by weight, at most about 12% by weight, or atmost about 10% by weight) the redox agent.

In some embodiments, the compositions of this disclosure contain atleast one (e.g., two, three, four, or more) water soluble organicsolvent, such as a water soluble organic solvent selected from the groupof water soluble alcohols, water soluble ketones, water soluble esters,water soluble sulfones, and water soluble ethers (e.g., glycoldiethers).

Classes of water soluble alcohols include, but are not limited to,alkane diols (including, but not limited to, alkylene glycols), glycols,alkoxyalcohols (including, but not limited to, glycol monoethers),saturated aliphatic monohydric alcohols, unsaturated non-aromaticmonohydric alcohols, and low molecular weight alcohols containing a ringstructure (e.g., those having a molecular weight less than 500 g/mol,less than 400 g/mol, less than 300 g/mol, less than 200 g/mol, or lessthan 100 g/mol).

Examples of water soluble alkane diols include, but are not limited to,2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol,1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol,and alkylene glycols.

Examples of water soluble alkylene glycols include, but are not limitedto, ethylene glycol, propylene glycol, hexylene glycol, diethyleneglycol, dipropylene glycol, triethylene glycol and tetraethyleneglycol.

Examples of water soluble alkoxyalcohols include, but are not limitedto, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol,1-methoxy-2-butanol, and water soluble alkylene glycol monoethers.

Examples of water soluble alkylene glycol monoethers include, but arenot limited to, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycolmonoisopropyl ether, ethylene glycol mono n-butyl ether, diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, diethyleneglycol monobutyl ether, triethylene glycol monomethyl ether, triethyleneglycol monoethyl ether, triethylene glycol monobutyl ether,1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol,2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropyleneglycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyleneglycol mono n-propyl ether, tripropylene glycol monoethyl ether,tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether,and diethylene glycol monobenzyl ether.

Examples of water soluble saturated aliphatic monohydric alcoholsinclude, but are not limited to, methanol, ethanol, n-propyl alcohol,isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butylalcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol.

Examples of water soluble unsaturated non-aromatic monohydric alcoholsinclude, but are not limited to, allyl alcohol, propargyl alcohol,2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

Examples of water soluble, low molecular weight alcohols containing aring structure include, but are not limited to, tetrahydrofurfurylalcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

Examples of water soluble ketones include, but are not limited to,acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone,diacetone alcohol, 2-butanone, 2,5-hexanedione, 1,4-cyclohexanedione,3-hydroxyacetophenone, and 1,3-cyclohexanedione.

Examples of water soluble esters include, but are not limited to, ethylacetate, and glycol monoesters (such as ethylene glycol monoacetate,diethylene glycol monoacetate, and glycol monoether monoesters such aspropylene glycol monomethyl ether acetate, ethylene glycol monomethylether acetate, propylene glycol monoethyl ether acetate, and ethyleneglycol monoethyl ether acetate).

Examples of water soluble sulfones include, but are not limited to,sulfolane and dimethyl sulfone.

Examples of water soluble ethers include, but are not limited to,alkoxyalcohols (e.g., alkylene glycol monoethers), such as thosedescribed above.

In some embodiments, the cleaning compositions of this disclosureinclude at least about 60% by weight (e.g., at least about 65% byweight, at least about 70% by weight, or at least about 75% by weight)and/or at most about 95% by weight (e.g., at most about 90% by weight,at most about 85% by weight, or at most about 80% by weight) the atleast one water soluble organic solvent.

The cleaning compositions of the present disclosure further includewater. Preferably, the water is de-ionized and ultra-pure, contains noorganic contaminants and has a minimum resistivity of about 4 to about17 mega Ohms. More preferably, the resistivity of the water is at least17 mega Ohms.

In some embodiments, the cleaning compositions of this disclosureinclude at least about 5% by weight (e.g., at least about 8% by weight,at least about 12% by weight, or at least about 16% by weight) and/or atmost about 28% by weight (e.g., at most about 24% by weight, at mostabout 20% by weight, or at most about 18% by weight) water.

Metal-containing additives contemplated for use in the cleaningcompositions of the disclosure include metals selected from Group 2Ametals, Group 3B metals, Group 4B metals, Group 5B metals, andlanthanide metals. In some embodiments, the metal is Ca, Ba, Ti, Hf, Sr,La, Ce, W, V, Nb, or Ta. In some embodiments, the metal is selected fromGroup 4B metals (such as Ti or Hf).

The metal-containing additive can be in the form of a metal halide, ametal hydroxide, a metal boride, a metal alkoxide, a metal oxide, or ametal-containing ammonium salt. In some embodiments, themetal-containing additive is an ammonium salt. The ammonium salt can bea salt of formula (I): (NH₄)_(m)MX_(n) (I); in which m is 1, 2, 3, or 4;n is 1, 2, 3, 4, 5, or 6; M is a metal ion (such as an ion of a Group 2Ametal, Group 3B metal, Group 4B metal, Group 5B metal, or lanthanidemetal); and X is a halide ion (e.g., F, Cl, Br, or I). In certainembodiments, the metal-containing additive is ammoniumhexafluorotitanate ((NH₄)₂TiF₆). Examples of metal-containing additivescan include tungsten borides, Ca(OH)₂, BaCl₂, SrCl₂, LaCl₃, CeCl₃,(NH₄)₂TiF₆, BaTiO₃, Ti(OEt)₄, Ti(OCH(CH₃)₂)₄, HfO₂, V₂O₅, Nb₂O₅, andTaF₃.

In some embodiments, the metal-containing additive can be in an amountof at least about 0.001% by weight (e.g., at least about 0.002% byweight, at least about 0.004% by weight, at least about 0.006% byweight, at least about 0.008% by weight, or at least about 0.01% byweight) and/or at most about 0.5% by weight (e.g., at most about 0.4% byweight, at most about 0.3% by weight, at most about 0.2% by weight, atmost about 0.1% by weight, at most about 0.08% by weight, at most about0.06% by weight, at most about 0.04% by weight, at most about 0.02% byweight, or at most about 0.01% by weight) of the cleaning composition.Without wishing to be bound by theory, it is believed that including themetal-containing additive in the amount specified above in a cleaningcomposition can reduce the corrosion effects of the composition, i.e.,lowering the etch rate of the cleaning composition towards the exposedsubstrate materials (e.g., exposed metals or dielectric materials) thatare not intended to be removed during the cleaning process.

In general, the cleaning compositions of this disclosure can include atleast one (e.g., two, three, or four) cyclic amine. In some embodiments,the at least one cyclic amine includes a cyclic amine of formula (I):

in which n is 1, 2, or 3; m is 1, 2, or 3; each of R₁-R₁₀,independently, is H, C₁-C₆ alkyl, or aryl; and L is —O—, —S—,—N(R_(a))—, or —C(R_(a)R_(b))—, in which each of R_(a) and R_(b),independently, is H, C₁-C₆ alkyl, or aryl; and R₁₁ is H or together withR_(a) forms a second bond between L and the C atom to which R₁₁ isattached. As used herein, the term “C₁₋₆ alkyl” refers to a saturatedhydrocarbon group that can be straight-chained or branched and can have1 to 6 carbons. As used herein, the term “aryl” refers to a hydrocarbongroup having one or more aromatic rings (e.g., two or more fusedaromatic rings). In some embodiments, the aryl group can have 6-10 ringcarbons.

In some embodiments, L in formula (I) is —N(R_(a))—. In suchembodiments, n can be 2; m can be 1 or 3; each of R₁-R₁₀ can be H; andR₁₁, together with R_(a), can form a second bond between L and the Catom to which R₁₁ is attached. Examples of such amines include1,8-diazabicyclo[5.4.0]-7-undecene (DBU;

and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN;

In some embodiments, L in formula (I) is —C(R_(a)R_(b))—. In suchembodiments, n can be 2; m can be 2; and each of R₁-R₁₁ can be H. Anexample of such amine is octahydro-2H-quinolizine

Without wishing to be bound by theory, it is believed that the cyclicamine described herein can reduce the corrosion effects of a cleaningcomposition that is primary based on organic solvents (e.g., containingfrom about 60% by weight to about 95% by weight organic solvents). Forexample, the cyclic amine can help lower the etch rate of such acleaning composition towards the exposed substrate materials (e.g.,exposed metals (such as cobalt) or dielectric materials) that are notintended to be removed during the cleaning process.

In some embodiments, the cyclic amine can be in an amount of at leastabout 0.1% by weight (e.g., at least about 0.2% by weight, at leastabout 0.3% by weight, at least about 0.4% by weight, at least about 0.5%by weight, at least about 0.6% by weight, at least about 0.7% by weight,at least about 0.8% by weight, at least about 0.9% by weight, or atleast about 1% by weight) and/or at most about 2% by weight (e.g., atmost about 1.9% by weight, at most about 1.8% by weight, at most about1.7% by weight, at most about 1.6% by weight, at most about 1.5% byweight, at most about 1.4% by weight, at most about 1.3% by weight, atmost about 1.2% by weight, or at most about 1.1% by weight) of thecleaning composition. Without wishing to be bound by theory, it isbelieved that including the cyclic amine described herein in the amountspecified above in a cleaning composition can reduce the corrosioneffects of the composition, i.e., lowering the etch rate of the cleaningcomposition towards the exposed substrate materials (e.g., exposedmetals (such as cobalt) or dielectric materials) that are not intendedto be removed during the cleaning process.

The cleaning compositions of this disclosure can optionally contain atleast one (e.g., two, three, or four) cleaning additive to improve theircleaning capability (e.g., removing etch or ashing residues) and/orreduce their corrosion effects. In some embodiments, the cleaningadditive can be a sulfur-containing additive or an amino acid. In someembodiments, the cleaning compositions can include both asulfur-containing additive and an amino acid.

Sulfur-containing additives contemplated for use in the cleaningcompositions of the disclosure are not particularly limited. In someembodiments, the sulfur-containing additive is a molecule bearing athiol moiety (i.e., SH) or thioether moiety (e.g., SR in which R isC₁-C₁₀ alkyl). In some embodiments, the sulfur-containing additive canbe an alcohol, an acid, an amine, or a heterocyclic compound thatcontains a thiol or thioether moiety. Examples of sulfur-containingadditives include, but are not limited to,3-amino-5-mercapto-1H-1,2,4-triazole; β-mercaptoethanol;3-amino-5-methylthio-1H-1,2,4-triazole; 1-phenyl-1H-tetrazole-5-thiol;4-methyl-4H-1,2,4-triazole-3-thiol; 2-pyridinethiol;3-mercapto-propionic acid, and the like. In some embodiments, thesulfur-containing additive may exclude sulfur-containing organic acids.

In some embodiments, the sulfur-containing additive can be in an amountof at least about 0.01% by weight (e.g., at least about 0.02% by weight,at least about 0.04% by weight, at least about 0.05% by weight, at leastabout 0.06% by weight, or at least about 0.08% by weight) and/or at mostabout 0.15% by weight (e.g., at most about 0.14% by weight, at mostabout 0.12% by weight, at most about 0.1% by weight, at most about 0.08%by weight, or at most about 0.07% by weight) of the cleaningcomposition. Without wishing to be bound by theory, it is believed thatincluding the sulfur-containing additive in the amount specified abovein a cleaning composition can improve the cleaning capability of thecomposition for removing post etch and/or post ashing residues and/orlower the etch rate of the cleaning composition towards the exposedsubstrate materials (e.g., exposed metals or dielectric materials) thatare not intended to be removed during the cleaning process.

In some embodiments, the cleaning additive can include at least one(e.g., two, three, or four) amino acid (e.g., glycine). The amino acidcan be a naturally occurring amino acid or a non-naturally occurringamino acid (e.g., a synthetic amino acid). The amino acid can be a D- orL-amino acid.

In some embodiments, the amino acid can be in an amount of at leastabout 0.01% by weight (e.g., at least about 0.02% by weight, at leastabout 0.04% by weight, at least about 0.05% by weight, at least about0.06% by weight, or at least about 0.08% by weight) and/or at most about0.15% by weight (e.g., at most about 0.14% by weight, at most about0.12% by weight, at most about 0.1% by weight, at most about 0.08% byweight, or at most about 0.07% by weight) of the cleaning composition.Without wishing to be bound by theory, it is believed that including theamino acid in the amount specified above in a cleaning composition canimprove the cleaning capability of the composition for removing postetch and/or post ashing residues and/or lower the etch rate of thecleaning composition towards the exposed substrate materials (e.g.,exposed metals or dielectric materials) that are not intended to beremoved during the cleaning process.

In some embodiments, the cleaning compositions of this disclosure cancontain one or more (e.g., two, three, or four) organic acids. Theorganic acids can be used in the cleaning compositions in the presenceor absence of the cleaning additive mentioned above (e.g., thesulfur-containing additive or the amino acid). Organic acidscontemplated for use in the cleaning compositions of the disclosureinclude carboxylic acids and sulfonic acids. Exemplary carboxylic acidcontemplated for use in the compositions of the disclosure include, butare not limited to, monocarboxylic acids, bicarboxylic acids,tricarboxylic acids, α-hydroxyacids and β-hydroxyacids of monocarboxylicacids, α-hydroxyacids or β-hydroxyacids of bicarboxylic acids, andα-hydroxyacids and β-hydroxyacids of tricarboxylic acids. Examples ofsuitable carboxylic acids include, but are not limited to, citric acid,maleic acid, fumaric acid, lactic acid, glycolic acid, oxalic acid,tartaric acid, succinic acid, and benzoic acid. Examples of suitablesulfonic acids include, but are not limited to, methanesulfonic acid,trifluoromethanesulfonic acid, ethanesulfonic acid,trifluoroethanesulfonic acid, perfluoroethylsulfonic acid,perfluoro(ethoxyethane)sulfonic acid, perfluoro(methoxyethane)sulfonicacid, dodecylsulfonic acid, perfluorododecylsulfonic acid,butanesulfonic acid, perfluorobutanesulfonic acid, propanesulfonic acid,perfluoropropanesulfonic acid, octylsulfonic acid,pefluorooctanesulfonic acid, methanedisulfonic acid,2-methylpropanesulfonic acid, cyclohexylsulfonic acid, camphorsulfonicacids, perfluorohexanesulfonic acid, ethanedisulfonic acid,benzylsulfonic acid, hydroxyphenylmethanesulfonic acid,naphthylmethanesulfonic acid, norbornanesulfonic acids, benzenesulfonicacid, chlorobenzenesulfonic acids, bromobenzenesulfonic acids,fluorobenzenesulfonic acids, hydroxybenzenesulfonic acids,nitrobenzenesulfonic acids, 2-hydroxy-5-sulfobenzoic acid,benzenedisulfonic acids, toluenesulfonic acids (e.g., p-toluenesulfonicacid), methylchlorobenzenesulfonic acids, dodecylbenzenesulfonic acids,butylbenzenesulfonic acids, cyclohexylbenzenesulfonic acids,picrylsulfonic acid, dichlorobenzenesulfonic acids,dibromobenzenesulfonic acids, and 2,4,5-trichlorobenzenesulfonic acid.

In some embodiments, the organic acid can be in an amount of at leastabout 0.01% by weight (e.g., at least about 0.05% by weight, at leastabout 0.1% by weight, at least about 0.12% by weight, at least about0.14% by weight, at least about 0.16% by weight, at least about 0.18% byweight, or at least about 0.2% by weight) and/or at most about 0.5% byweight (e.g., at most about 0.4% by weight, at most about 0.3% byweight, at most about 0.2% by weight, at most about 0.18% by weight, orat most about 0.16% by weight) of the cleaning composition. Withoutwishing to be bound by theory, it is believed that the organic acid canserve as a chelating agent in the cleaning composition to facilitate theremoval of post etch and/or post ashing residues.

The cleaning compositions of this disclosure optionally contain at leastone pH adjusting agent (e.g., an acid or a base) to control the pH tofrom about 7 to about 12. In some embodiments, the compositions of thisdisclosure can have a pH of at least about 7 (e.g., at least about 7.5,at least about 8, or at least about 8.5) to at most about 12 (e.g., atmost about 11.5, at most about 11, at most about 10.5, at most about 10,at most about 9.5, at most about 9). Without wishing to be bound bytheory, it is believed that a cleaning composition having a pH higherthan 12 decreases the plasma etch residue cleaning to an impracticallevel for complete cleaning and that a pH lower than 7 would increasethe etch rate of certain metals or dielectric materials to anundesirable level. The effective pH can vary depending on the types andamounts of the ingredients used in the cleaning compositions describedherein.

The amount of the pH adjusting agent required, if any, can vary as theconcentrations of the other components are varied in differentformulations, particularly the hydroxylamine and the organic acid, andas a function of the molecular weight of the particular pH adjustingagent employed. In general, the pH adjusting agent concentration rangesfrom about 0.1% to about 3% by weight of the cleaning composition. Insome embodiments, the cleaning compositions of this disclosure includeat least about 0.1% by weight (e.g., at least about 0.5% by weight, atleast about 1% by weight, or at least about 1.5% by weight) and/or atmost about 3% by weight (e.g., at most about 2.5% by weight, at mostabout 2% by weight, or at most about 1.5% by weight) the pH adjustingagent.

In general, the pH adjusting agent is free of any metal ion (except fora trace amount of metal ion impurities). Suitable metal ion free pHadjusting agents include ammonium hydroxide, quaternary ammoniumhydroxides, monoamines (including alkanolamines), imines (such as1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and1,5-diazabicyclo[4.3.0]-5-nonene (DBN)), and guanidine salts (such asguanidine carbonate).

Examples of suitable quaternary ammonium hydroxides include, but are notlimited to, tetramethyl ammonium hydroxide, tetraethyl ammoniumhydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammoniumhydroxide, dimethyldiethylammonium hydroxide, choline,tetraethanolammonium hydroxide, benzyltrimethylammonium hydroxide,benzyltriethylammonium hydroxide, and benzyltributylammonium hydroxide.

Examples of suitable monoamines include, but are not limited to,triethylamine, tributylamine, tripentylamine, ethanolamine,diethanolamine, diethylamine, butylamine, dibutylamine, and benzylamine.

In addition, in some embodiments, the cleaning compositions of thepresent disclosure may contain additives such as, additional pHadjusting agents, corrosion inhibitors (e.g., a substituted orunsubstituted benzotriazole), surfactants, additional organic solvents,biocides, and defoaming agents as optional components.

Examples of suitable defoaming agents include polysiloxane defoamers(e.g., polydimethylsiloxane), polyethylene glycol methyl ether polymers,ethylene oxide/propylene oxide copolymers, and glycidyl ether cappedacetylenic diol ethoxylates (such as those described in U.S. Pat. No.6,717,019, herein incorporated by reference).

In some embodiments, the cleaning compositions of the present disclosuremay specifically exclude one or more of the additive components, in anycombination, if more than one. Such excluded components are selectedfrom the group consisting of polymers, oxygen scavengers, quaternaryammonium hydroxides, amines, alkali metal and alkaline earth bases (suchas NaOH, KOH, LiOH, magnesium hydroxide, and calcium hydroxide),surfactants other than a defoamer, fluoride containing compounds,oxidizing agents (e.g., peroxides, hydrogen peroxide, ferric nitrate,potassium iodate, potassium permanganate, nitric acid, ammoniumchlorite, ammonium chlorate, ammonium iodate, ammonium perborate,ammonium perchlorate, ammonium periodate, ammonium persulfate,tetramethylammonium chlorite, tetramethylammonium chlorate,tetramethylammonium iodate, tetramethylammonium perborate,tetramethylammonium perchlorate, tetramethylammonium periodate,tetramethylammonium persulfate, urea hydrogen peroxide, and peraceticacid), abrasives (e.g., abrasive particles), silicates,hydroxycarboxylic acids, carboxylic and polycarboxylic acids (e.g.,those lacking amino groups), non-azole corrosion inhibitors, bufferingagents, guanidine, guanidine salts, inorganic acids (e.g., sulfonicacids, sulfuric acid, sulfurous acid, nitrous acid, nitric acid,phosphorous acid, and phosphoric acid), pyrrolidone, polyvinylpyrrolidone, metal halides, metal halides of the formula W_(z)MX_(y),wherein W is selected from H, an alkali or alkaline earth metal, and ametal-ion-free hydroxide base moiety; M is a metal selected from thegroup consisting of Si, Ge, Sn, Pt, P, B, Au, Ir, Os, Cr, Ti, Zr, Rh, Ruand Sb; y is from 4 to 6; and z is 1, 2, or 3, and corrosion inhibitorsother than those described in this disclosure.

In some embodiments, the cleaning compositions of the present disclosureare not specifically designed to remove bulk photoresist films fromsemiconductor substrates. Rather, the cleaning compositions of thepresent disclosure can be designed to remove all residues after bulkresist removal by dry or wet stripping methods. Therefore, in someembodiments, the cleaning method of the present disclosure is preferablyemployed after a dry or wet photoresist stripping process. Thisphotoresist stripping process is generally preceded by a patterntransfer process, such as an etch or implant process, or is done tocorrect mask errors before pattern transfer. The chemical makeup of theresidue will depend on the process or processes preceding the cleaningstep.

Any suitable dry stripping process can be used to remove bulk resistfrom semiconductor substrates. Examples of suitable dry strippingprocesses include oxygen based plasma ashing, such as a fluorine/oxygenplasma or a N₂/H₂ plasma, ozone gas phase-treatment, fluorine plasmatreatment, hot H₂ gas treatment (such as that described in U.S. Pat. No.5,691,117 incorporated herein by reference in its entirety), and thelike. In addition, any suitable conventional organic wet strippingsolution known to a person skilled in the art can be used to remove bulkresist from semiconductor substrates.

A preferred stripping process used in combination with the cleaningmethod of the present disclosure is a dry stripping process. Preferably,this dry stripping process is an oxygen based plasma ashing process.Such a process removes most of the photoresist from the semiconductorsubstrate by applying a reactive-oxygen atmosphere at elevatedtemperatures (typically 250° C.) at vacuum conditions (i.e., 1 torr).Organic materials are oxidized by this process and are removed with theprocess gas. However, this process does not remove inorganic ororganometallic contamination from the semiconductor substrate. Asubsequent cleaning of the semiconductor substrate with the cleaningcomposition of the present disclosure is typically necessary to removethose residues.

In some embodiments, this disclosure features methods of cleaningresidues from a semiconductor substrate. Such methods can be performed,for example, by contacting a semiconductor substrate containing postetch residues and/or post ashing residues with a cleaning compositiondescribed herein. The method can further include rinsing thesemiconductor substrate with a rinse solvent after the contacting stepand/or drying the semiconductor substrate after the rinsing step. Insome embodiments, the semiconductor substrate can further include amaterial (e.g., an exposed material) or a layer of the material, wherethe material is selected from the group consisting of Cu, Co, W, AlOx,AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx, ZrOx, HfOx, and TaOx.

In some embodiments, the cleaning method includes the steps of:

-   -   (A) providing a semiconductor substrate containing post etch        and/or post ashing residues;    -   (B) contacting said semiconductor substrate with a cleaning        composition described herein;    -   (C) rinsing said semiconductor substrate with a suitable rinse        solvent; and    -   (D) optionally, drying said semiconductor substrate by any means        that removes the rinse solvent and does not compromise the        integrity of said semiconductor substrate.        In some embodiments, the cleaning method further includes        forming a semiconductor device (e.g., an integrated circuit        device such as a semiconductor chip) from the semiconductor        substrate obtained by the method described above.

The semiconductor substrates to be cleaned in this method can containorganic and organometallic residues, and additionally, a range of metaloxides that need to be removed. Semiconductor substrates typically areconstructed of silicon, silicon germanium, Group III-V compounds likeGaAs, or any combination thereof. The semiconductor substrates canadditionally contain exposed integrated circuit structures such asinterconnect features (e.g., metal lines and dielectric materials).Metals and metal alloys used for interconnect features include, but arenot limited to, aluminum, aluminum alloyed with copper, copper,titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride,tungsten, and their alloys. Said semiconductor substrate can alsocontain layers of interlayer dielectrics, silicon oxide, siliconnitride, silicon carbide, titanium oxide, and carbon doped siliconoxides.

The semiconductor substrate can be contacted with a cleaning compositionby any suitable method, such as placing the cleaning composition into atank and immersing and/or submerging the semiconductor substrates intothe cleaning composition, spraying the cleaning composition onto thesemiconductor substrate, streaming the cleaning composition onto thesemiconductor substrate, or any combinations thereof. Preferably, thesemiconductor substrates are immersed into the cleaning composition.

The cleaning compositions of the present disclosure may be effectivelyused up to a temperature of about 90° C. (e.g., from about 25° C. toabout 80° C., from about 30° C. to about 60° C., or from about 40° C. toabout 60° C.).

Similarly, cleaning times can vary over a wide range depending on theparticular cleaning method and temperature employed. When cleaning in animmersion batch type process, a suitable time range is, for example, upto about 60 minutes (e.g., from about 1 minute to about 60 minutes, fromabout 3 minutes to about 20 minutes, or from about 4 minutes to about 15minutes).

Cleaning times for a single wafer process may range from about 10seconds to about 5 minutes (e.g., from about 15 seconds to about 4minutes, from about 15 seconds to about 3 minutes, or from about 20seconds to about 2 minutes).

To further promote the cleaning ability of the cleaning composition ofthe present disclosure, mechanical agitation means may be employed.Examples of suitable agitation means include circulation of the cleaningcomposition over the substrate, streaming or spraying the cleaningcomposition over the substrate, and ultrasonic or megasonic agitationduring the cleaning process. The orientation of the semiconductorsubstrate relative to the ground may be at any angle. Horizontal orvertical orientations are preferred.

The cleaning compositions of the present disclosure can be used inconventional cleaning tools known to those skilled in the art. Asignificant advantage of the compositions of the present disclosure isthat they include relatively non-toxic, non-corrosive, and non-reactivecomponents in whole or in part, whereby the compositions are stable in awide range of temperatures and process times. The compositions of thepresent disclosure are chemically compatible with practically allmaterials used to construct existing and proposed semiconductor wafercleaning process tools for batch and single wafer cleaning.

Subsequent to the cleaning, the semiconductor substrate can be rinsedwith a suitable rinse solvent for about 5 seconds up to about 5 minuteswith or without agitation means. Examples of suitable rinse solventsinclude, but are not limited to, deionized (DI) water, methanol,ethanol, isopropyl alcohol, N-methylpyrrolidinone, gamma-butyrolactone,dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl etheracetate. Alternatively, aqueous rinses with pH >8 (such as diluteaqueous ammonium hydroxide) may be employed. Preferred examples of rinsesolvents include, but are not limited to, dilute aqueous ammoniumhydroxide, DI water, methanol, ethanol, and isopropyl alcohol. Thesolvent may be applied using means similar to that used in applying acleaning composition described herein. The cleaning composition may havebeen removed from the semiconductor substrate prior to the start of therinsing step or it may still be in contact with the semiconductorsubstrate at the start of the rinsing step. Preferably, the temperatureemployed in the rinsing step is between 16° C. and 27° C.

Optionally, the semiconductor substrate is dried after the rinsing step.Any suitable drying means known in the art may be employed. Examples ofsuitable drying means include spin drying, flowing a dry gas across thesemiconductor substrate, heating the semiconductor substrate with aheating means such as a hotplate or infrared lamp, Marangoni drying,Rotagoni drying, IPA drying, or any combinations thereof. Drying timeswill be dependent on the specific method employed but are typically onthe order of 30 seconds up to several minutes.

In some embodiments, a method of manufacturing an integrated deviceusing a cleaning composition described herein can include the followingsteps. First, a layer of a photoresist is applied to a semiconductorsubstrate. The semiconductor substrate thus obtained can then undergo apattern transfer process, such as an etch or implant process, to form anintegrated circuit. The bulk of the photoresist can then be removed by adry or wet stripping method (e.g., an oxygen based plasma ashingprocess). Remaining residues on the semiconductor substrate can then beremoved using a cleaning composition described herein in the mannerdescribed above. The semiconductor substrate can subsequently beprocessed to form one or more additional circuits on the substrate orcan be processed to form into a semiconductor chip by, for example,assembling (e.g., dicing and bonding) and packaging (e.g., chipsealing).

The contents of all publications cited herein (e.g., patents, patentapplication publications, and articles) are hereby incorporated byreference in their entirety.

EXAMPLES

The present disclosure is illustrated in more detail with reference tothe following examples, which are for illustrative purposes and shouldnot be construed as limiting the scope of the present disclosure. Anypercentages listed are by weight (wt %) unless otherwise specified. Alletch rates listed are average etch rates unless otherwise specified.Controlled stirring during testing was done with a 1 inch stirring barat 300 rpm unless otherwise noted.

General Procedure 1 Formulation Blending

Compositions of the disclosure were prepared by mixing, while stirring,the organic solvents and ultra-pure deionized water (DIW). After auniform solution was achieved, the remaining components were added. Allcomponents used were commercially available and of high purity.

General Procedure 2 Cleaning Evaluation with Beaker Test

The cleaning of PER (Post Etch Residue) from a substrate was carried outwith the above-described cleaning compositions using a multilayeredsubstrate containing Co/TiN/Ti/TiOx/ILD.

The test coupons were held using 4″ long plastic locking tweezers,whereby the coupon could then be suspended into a 500 ml volume glassbeaker containing approximately 200 milliliters of a cleaningcomposition of the present disclosure. Prior to immersion of the couponinto the cleaning composition, the composition was pre-heated to thedesired test condition temperature (typically 40° C. or 65° C. as noted)with controlled stirring. The cleaning tests were then carried out byplacing the coupon which was held by the plastic tweezers into theheated composition in such a way that the PER layer containing side ofthe coupon faced the stir bar. The coupon was left static in thecleaning composition for a time period (typically 5 to 15 minutes) whilethe composition was kept at the test temperature under controlledstirring. When the desired cleaning time was completed, the coupon wasquickly removed from the cleaning composition and placed in a 500 mlpyrex beaker filled with approximately 400 ml of DI water at ambienttemperature (−17° C.) with gentle stirring. The coupon was left in thebeaker of DI water for approximately 6 seconds, and then quicklyremoved, and transferred to a glass beaker containing a similar amountof IPA for about 30 seconds of gentle stirring. The coupon wasimmediately exposed to a nitrogen gas stream from a hand held nitrogenblowing gun, which caused any droplets on the coupon surface to be blownoff the coupon, and further, to completely dry the coupon devicesurface. Following this final nitrogen drying step, the coupon wasremoved from the plastic tweezers holder and placed into a coveredplastic carrier with the device side up for short term storage nogreater than about 2 hours. The scanning electron microscopy (SEM)images were then collected for key features on the cleaned test coupondevice surface.

General Procedure 3 Materials Compatibility Evaluation with Beaker Test

The blanket Co on silicon substrate (i.e., silicon wafer), TiOx onsilicon substrate, TiN on silicon substrate, AlOx on silicon substrate,and/or W alloy on silicon substrate were diced into approximately 1inch×1 inch square test coupons for the materials compatibility tests.The test coupons were initially measured for thickness or sheetresistance by the 4-point probe, CDE Resmap 273 for a metallic film(Co), or by Elipsometry for a dielectric film (TiOx, TiN, or AlOx) usinga Woollam M-2000X. The test coupons were then installed on the 4″ longplastic locking tweezers and treated as described in the cleaningprocedure in General Procedure 2 (unless otherwise specified) with theCo, W alloy, TiOx, TiN, or AlOx layer containing side of the couponfaced the stir bar for 10 minutes.

After the final nitrogen drying step, the coupon was removed from theplastic tweezers holder and placed into a covered plastic carrier. Thepost-thickness or sheet resistance was then collected on thepost-processing test coupon surface by the 4-point probe, CDE Resmap 273for a metallic film (Co or W alloy) or by Elipsometry for dielectricfilm (TiOx, TiN, or AlOx) using a Woollam M-2000X.

Formulation Examples FE-1 to FE-6

Cleaning formulations FE-1 to FE-6 (all of which contained asulfur-containing additive and a metal-containing additive) wereprepared by General Procedure 1. Their compositions are summarized inTable 1.

TABLE 1 First Second Sulfur- Metal- Hydroxyl- organic organic containingcontaining Organic Ex. amine solvent solvent additive additive AmineWater acid PH FE-1 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ None 16% MSA 8.40glycol 10% pyridinethiol 0.008% 0.173% 64.75% 0.067% FE-2 9.00% HexDEGBE 2- (NH₄)₂TiF₆ DTPA 1% MSA 8.38 glycol 10% pyridinethiol 0.008%(0.5%) 0.173% 64.25% 0.067% FE-3 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ 5MBTA 16%MSA 8.43 glycol 10% pyridinethiol 0.008% (0.25%) 0.173% 64.5% 0.067%FE-4 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ DBU 16% MSA 9.16 glycol 10%pyridinethiol 0.008% (0.35%) 0.173% 64.4% 0.067% FE-5 9.00% Hex DEGBE 2-(NH₄)₂TiF₆ DBU 16% MSA 8.55 glycol 10% pyridinethiol 0.008% (0.175%)0.173% 64.575% 0.067% FE-6 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ NH₄OH 16% MSA9.16 glycol 10% pyridinethiol 0.008% (0.8%) 0.173% 63.95% 0.067% DEGBE =diethylene glycol butyl ether; Hex glycol = hexylene glycol; MSA =methanesulfonic acid; DTPA = diethylenetriamine pentaacetic acid; 5MBTA= 5-methylbenzotriazole; DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene.

Examples 1-6 Compatibility of Cleaners with Exposed Cobalt

Formulations FE-1 to FE-6 were tested for cobalt corrosion inhibitionability according to General Procedure 2 using a patterned siliconsubstrate containing a cobalt layer below an exposed titanium layer. Theloss of exposed cobalt by the cleaning compositions (i.e., the numbersof exposed cobalt removed by the cleaning compositions) was measured andis shown in Table 2.

TABLE 2 Formulation Example Co Loss (counts) FE-1 0.9 ± 0.7 FE-2 4.1 ±2.3 FE-3 0.4 ± 0.5 FE-4 0.0 ± 0.0 FE-5 0.2 ± 0.4 FE-6 2.1 ± 1.6

The data in Table 2 show that, surprisingly, formulations FE-4 and FE-5(which contained a cyclic amine of formula (I)) exhibited very low or nocobalt corrosion effect when they were used to clean the post etchresidue on a patterned silicon substrate. Formulations FE-1 (whichcontained no amine), FE-2 (which contained a tertiary amine), and FE-3(which contained a cyclic amine different from that of formula (I))exhibited higher levels cobalt corrosion effect than formulation FE-1.

In addition, FE-4 and FE-6 had the same pH but contained different basiccompounds. The results show that FE-4 (which contained a cyclic amine offormula (I)) exhibited significantly better cobalt corrosion inhibitionthan FE-6 (which contained ammonium hydroxide, not a cyclic amine offormula (I)). These results suggest that the cyclic amine of formula (I)contributed to the superior cobalt corrosion inhibition effect of FE-4.

Formulation Examples FE-7 to FE-12

Cleaning formulations FE-7 to FE-12 (all of which contained asulfur-containing additive and a metal containing additive) wereprepared by General Procedure 1. Their compositions are summarized inTable 3. In particular, formulations FE-7 to FE-12 contained anincreasing amount of DBU.

TABLE 3 First Second Sulfur- Metal- Hydroxyl- organic organic containingcontaining Organic Ex. amine solvent solvent additive additive AmineWater acid PH FE-7 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ DBU 16% MSA 8.3 glycol10% pyridinethiol 0.008% (0.200%) 0.173% 64.55% 0.067% FE-8 9.00% HexDEGBE 2- (NH₄)₂TiF₆ DBU 16% MSA 8.6 glycol 10% pyridinethiol 0.008%(0.264%) 0.173% 64.49% 0.067% FE-9 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ DBU 16%MSA 8.7 glycol 10% pyridinethiol 0.008% (0.297%) 0.173% 64.45% 0.067%FE- 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ DBU 16% MSA 9.1 10 glycol 10%pyridinethiol 0.008% (0.350%) 0.173% 64.4% 0.067% FE- 9.00% Hex DEGBE 2-(NH₄)₂TiF₆ DBU 16% MSA 9.2 11 glycol 10% pyridinethiol 0.008% (0.363%)0.173% 64.39% 0.067% FE- 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ DBU 16% MSA 9.812 glycol 10% pyridinethiol 0.008% (0.396%) 0.173% 64.35% 0.067%

Examples 7-12 Compatibility of Cleaners with Exposed Metals orDielectrics

Formulations FE-7 to FE-12 were tested for materials compatibilityaccording to General Procedure 2 using a patterned silicon substratecontaining exposed cobalt. Formulations FE-7 to FE-9, FE-11, and FE-12were tested for materials compatibility according to General Procedure 3using blanket films on silicon substrates at 65° C. for 4 minutes. Theloss of exposed cobalt on patterned silicon substrates by the cleaningcompositions (i.e., the numbers of exposed cobalt removed by thecleaning compositions) was measured and is shown in Table 4. The etchrates (ER) (Angstroms/minute) of W alloy, Co, AlOx, TiOx, and TiN asblanket films on silicon substrates by the cleaning formulations areshown in Table 5.

TABLE 4 Formulation Example Co Loss (counts) FE-7 0.2 ± 0.4 FE-8 0.0 ±0.0 FE-9 0.0 ± 0.0 FE-10 0.0 ± 0.0 FE-11 0.1 ± 0.3 FE-12 0.1 ± 0.3

TABLE 5 Formulation Example W alloy Co AlOx TiOx TiN FE-7 1.1 0.9 3.81.9 3.7 FE-8 0.3 0.4 ± 0.1 3.3 1.6 3.2 FE-9 0.8 0.5 ± 0.1 2.8 2.0 3.4FE-11 2.4 0.4 ± 0.1 2.7 2.7 3.9 FE-12 3.4 0.4 ± 0.1 1.8 3.2 4.4 The Walloy coated wafers were immersed in the cleaning formulations for 20minutes while the formulations were stirred at 250 rpm. The wafers werethen rinsed by isopropyl alcohol for 15 seconds twice and by DI waterfor one minute. The other wafers were immersed in the cleaningformulations for 10 minutes while the formulations were stirred at 250rpm. The wafers were then rinsed by isopropyl alcohol for 15 secondstwice and by DI water for 15 seconds.

The data in Table 4 show that cleaning formulations FE-7 to FE-12 allexhibited significantly reduced or substantially no cobalt loss oretching on a patterned silicon substrate. The data in Table 5 show thatcleaning formulations FE-7 to FE-9, FE-11, and FE-12 generally exhibitedreduced corrosion or etching of one or more of the metals or dielectrics(such as W alloy, Co, AlOx, TiOx, and TiN) as blanket films on siliconsubstrates.

Formulation Examples FE-13 to FE-16

Cleaning formulations FE-13 to FE-16 (all of which contained an aminoacid additive and a metal containing additive) were prepared by GeneralProcedure 1. Their compositions are summarized in Table 6. Specifically,formulations FE-13 to FE-16 had substantially the same compositionexcept for the amount of methanesulfonic acid (MSA) and, as a result,the pH.

TABLE 6 Hydroxyl- Hexylene Ex. amine glycol DEGBE (NH₄)₂TiF₆ Glycine MSADBU water pH FE-13 9% 65.0% 10.0% 0.0025% 0.03% 0.35% 0.35% 15.30% 9.1FE-14 9% 65.0% 10.0% 0.0025% 0.03% 0.28% 0.35% 15.38% 10.02 FE-15 9%65.0% 10.0% 0.0025% 0.03% 0.20% 0.35% 15.45% 11.26 FE-16 9% 65.0% 10.0%0.0025% 0.03% None 0.35% 15.65% 12.31

Examples 13-16 Compatibility of Cleaners with Exposed Metals

Formulations FE-13 to FE-16 were tested for materials compatibilityaccording to General Procedure 3 using blanket films on siliconsubstrates at 65° C. for 4 minutes. The etch rates (ER)(Angstroms/minute) of W alloy, Co, AlOx, TiOx, and TiN by the cleaningformulations are shown in Table 7.

TABLE 7 Formulation Example W alloy Co AlOx TiOx TiN FE-13 4.5 0.7 1.52.6 4.2 FE-14 >6.5 0.5 1.3 3.1 4.6 FE-15 >6.5 0.8 0.3 3.7 4.5 FE-16 >6.52.4 2.2 5.2 3.3

The data in Table 7 show that cleaning formulations FE-13 to FE-15generally exhibited reduced corrosion or etching of one or more of themetals or dielectrics (such as W alloy, Co, AlOx, TiOx, and TiN) asblanket films on silicon substrates when the pH values of the cleaningformulations were between 9 and 12. Formulation FE-16 exhibited a higherlevel of corrosion of the metals or dielectrics than FE-13 to FE-15 dueat least in part to its higher pH (i.e., >12).

Formulation Examples FE-17 to FE-18

Cleaning formulations FE-17 to FE-18 (all of which contained asulfur-containing additive and a metal containing additive) wereprepared by General Procedure 1. Their compositions are summarized inTable 8.

TABLE 8 First Second Sulfur- Metal- Hydroxyl- organic organic containingcontaining Organic Ex. amine solvent solvent additive additive AmineWater acid PH FE- 9.00% Hex DEGBE 2- (NH₄)₂TiF₆ DBU 16% MSA 9.9 17glycol 10% pyridinethiol 0.008% (0.35%) 0.173% 64.4% 0.067% FE- 9.00%Hex DEGBE 2- (NH₄)₂TiF₆ DBN 16% MSA 11.2 18 glycol 10% pyridinethiol0.008% (0.264%) 0.173% 64.49% 0.067% DBU =1,8-diazabicyclo[5.4.0]undec-7-ene; DBN =1,5-diazabicyclo[4.3.0]-5-nonene.

Examples 17-18 Compatibility of Cleaners with Exposed Metals

Formulations FE-17 to FE-18 were tested for cobalt compatibilityaccording to General Procedure 3 using blanket films on siliconsubstrates at 65° C. for 4 minutes. The etch rates (ER)(Angstroms/minute) of Co by the cleaning formulations are shown in Table9.

TABLE 9 Ex. Co FE-17 0.6 ± 0.2 FE-18 0.4 ± 0.2

The data in Table 9 show that formulations FE-17 and FE-18 (both ofwhich contained a cyclic amine of formula (I)) exhibited low corrosionor etching of exposed cobalt on silicon substrates. In other words, thisresults suggests that, like DBU, DBN also exhibited significantlyreduced cobalt corrosion or etching on a silicon substrate.

While the disclosure has been described in detail with reference tocertain embodiments thereof, it is understood that modifications andvariations are within the spirit and scope of that which is describedand claimed.

What is claimed is:
 1. A cleaning composition, comprising: 1) at leastone redox agent; 2) at least one water soluble organic solvent; 3) atleast one metal-containing additive; 4) at least one cyclic amine; and5) water.
 2. The composition of claim 1, wherein the composition has apH from about 7 to about
 12. 3. The composition of claim 1, wherein theat least one cyclic amine comprises a cyclic amine of formula (I):

in which n is 1, 2, or 3; m is 1, 2, or 3; each of R₁-R₁₀,independently, is H, C₁-C₆ alkyl, or aryl; and L is —O—, —S—,—N(R_(a))—, or —C(R_(a)R_(b))—, in which each of R_(a) and R_(b),independently, is H, C₁-C₆ alkyl, or aryl; and R₁₁ is H or together withR_(a) forms a second bond between L and the C atom to which R₁₁ isattached.
 4. The composition of claim 3, wherein the cyclic amine offormula (I) is


5. The composition of claim 1, wherein the at least one cyclic amine isfrom about 0.1% by weight to about 2% by weight of the composition. 6.The composition of claim 1, wherein the at least one redox agentcomprises hydroxylamine.
 7. The composition of claim 1, wherein the atleast one redox agent is from about 0.5% by weight to about 20% byweight of the composition.
 8. The composition of claim 1, wherein the atleast one water soluble organic solvent comprises two organic solvents.9. The composition of claim 8, wherein the two organic solvents are eachindependently selected from the group consisting of alkylene glycols andalkylene glycol ethers.
 10. The composition of claim 1, wherein the atleast one water soluble organic solvent is from about 60% by weight toabout 95% by weight of the composition.
 11. The composition of claim 1,wherein the at least one metal-containing additive comprises a metalhalide, a metal hydroxide, a metal boride, a metal alkoxide, a metaloxide, or a metal-containing ammonium salt.
 12. The composition of claim1, wherein the at least one metal-containing additive comprises a Group2A metal, a Group 3B metal, a Group 4B metal, a Group 5B metal, or alanthanide metal.
 13. The composition of claim 12, wherein the at leastone metal-containing additive comprises Ca, Ba, Ti, Hf, Sr, La, Ce, W,V, Nb, or Ta.
 14. The composition of claim 1, wherein the at least onemetal-containing additive comprises a tungsten boride, Ca(OH)₂, BaCl₂,SrCl₂, LaCl₃, CeCl₃, (NH₄)₂TiF₆, BaTiO₃, Ti(OEt)₄, Ti(OCH(CH₃)₂)₄, HfO₂,V₂O₅, Nb₂O₅, or TaF₃.
 15. The composition of claim 1, wherein the atleast one metal-containing additive is from about 0.001% by weight toabout 0.5% by weight of the composition.
 16. The composition of claim 1,wherein the water is from about 5% by weight to about 28% by weight ofthe composition.
 17. The composition of claim 1, further comprising a pHadjusting agent, the pH adjusting agent being different from the atleast one cyclic amine.
 18. The composition of claim 1, furthercomprising at least one cleaning additive.
 19. The composition of claim18, wherein the at least one cleaning additive comprises asulfur-containing additive.
 20. The composition of claim 19, wherein thesulfur-containing additive comprises a thiol or a thioether.
 21. Thecomposition of claim 20, wherein the sulfur-containing additivecomprises 3-amino-5-mercapto-1H-1,2,4-triazole, β-mercaptoethanol,3-amino-5-methylthio-1H-1,2,4-triazole, 1-phenyl-1H-tetrazole-5-thiol,4-methyl-4H-1,2,4-triazole-3-thiol, 2-pyridinethiol, or3-mercapto-propionic acid.
 22. The composition of claim 19, wherein thesulfur-containing additive is from about 0.01% by weight to about 0.15%by weight of the composition.
 23. The composition of claim 18, whereinthe at least one cleaning additive comprises an organic acid.
 24. Thecomposition of claim 23, wherein the organic acid comprises a carboxylicacid or a sulfonic acid.
 25. The composition of claim 23, wherein the atleast one organic acid is from about 0.1% by weight to about 0.5% byweight of the composition.
 26. The composition of claim 18, wherein theat least one cleaning additive comprises an amino acid.
 27. Thecomposition of claim 26, wherein the amino acid is glycine.
 28. Thecomposition of claim 26, wherein the amino acid is from about 0.01% byweight to about 0.15% by weight of the composition.
 29. A method,comprising: contacting a semiconductor substrate containing post etchresidues or post ashing residues with a cleaning composition of claim 1.30. The method of claim 29, wherein the semiconductor substrate furthercomprises a layer comprising a material selected from the groupconsisting of Cu, Co, W, AlOx, AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx,ZrOx, HfOx, and TaOx.
 31. The method of claim 29, further comprisingrinsing the semiconductor substrate with a rinse solvent after thecontacting step.
 32. The method of claim 31, further comprising dryingthe semiconductor substrate after the rinsing step.
 33. The method ofclaim 29, further comprising forming a semiconductor device from thesemiconductor substrate.